KR20110114232A - Block and graft copolymers of poly(alkylene carbonate) and various polymers - Google Patents

Abstract

The present invention relates to the production of poly (alkylene carbonates) by alternating copolymerization of carbon dioxide and epoxides. Specifically, in the presence of a polymer compound having a functional group of hydroxy or carboxylic acid, an epoxide compound and carbon dioxide using a metal trivalent compound prepared from a Salen-type ligand including a quaternary ammonium salt as a catalyst The present invention relates to a method for producing a block or graft copolymer of the polymer compound and poly (alkylene carbonate) by alternating copolymerization, and to a block or graft copolymer prepared by the method.

Description

Block and graft copolymers of poly (alkylene carbonate) and various polymers}

The present invention relates to the production of poly (alkylene carbonates) by alternating copolymerization of carbon dioxide and epoxides. Specifically, in the presence of a polymer compound having a functional group of hydroxy or carboxylic acid, an epoxide compound and carbon dioxide using a metal trivalent compound prepared from a Salen-type ligand including a quaternary ammonium salt as a catalyst The present invention relates to a method for producing a block or graft copolymer of the polymer compound and a poly (alkylene carbonate) by alternating copolymerization, and to a block or graft copolymer prepared by the method.

Poly (alkylene carbonate) is a biodegradable polymer that is useful as a packaging or coating, for example. The process for preparing poly (alkylene carbonate) from epoxide compound and carbon dioxide is environmentally friendly in that it does not use toxic compound, phosgene, and can obtain carbon dioxide at low cost.

Since the 1960s, many researchers have developed various types of catalysts for the production of poly (alkylene carbonates) from epoxide compounds and carbon dioxide. Recently, the investigator has studied a high activity synthesized from a Salen [Salen: ([H ₂ Salen = N , N ' -bis (3,5-dialkylsalicylidene) -1,2-ethylenediamine] -type ligand containing quaternary ammonium salts. , Highly Selective Catalyst [Seoul, Korea Patent Registration 10-0853358 (Registration Date: 2008.08.13); Lee, Fyeol, Sujith S, Eun-Kyung No, Min Jae-ki, Republic of Korea Patent Application 10-2008-0015454 (Application Date 2008.02.20) ; Eun Kyung Noh, Sung Jae Na, Sujith S, Sang-Wook Kim, and PCT / KR2008 / 002453 (filed April 30, 2008); Bun Yeoul Lee * J. Am . Chem . Soc . 2007 , 129 , 8082-8083 (2007.07.04); Sujith S, Jae Ki Min, Jong Eon Seong, Sung Jea Na, and Bun Yeoul Lee, Angew . Chem . Int . Ed . , 2008 , 47, 7306-7309 (2008.09.08)]. The catalyst disclosed by the present inventors exhibits high activity, high selectivity, can produce copolymers having high molecular weight, and can be polymerized even at high temperatures, thereby allowing commercial application. In addition, since the quaternary ammonium salt is included in the ligand, the catalyst can be easily separated from the copolymer after the carbon dioxide / epoxide copolymerization reaction and reused.

In addition, the present inventors closely analyze the structure of a catalyst which exhibits particularly high activity and high selectivity compared with other catalyst groups of the patent, and the structure is such that the oxygen atom is not coordinated with the nitrogen atom of Salen-ligand. It has been shown to have a unique structure that is not known previously (Example 1, Sung Jae Na, Sujith S, Anish Cyriac, Bo Eun Kim, Jina Yoo, Youn K. Kang, Su Jung Han, Chongmok Lee, and Bun Yeoul Lee * "Elucidation of the Structure of A Highly Active Catalytic System for CO ₂ / Epoxide Copolymerization: A Salen-Cobaltate Complex of An Unusual Binding Mode" Inorg . Chem . 2009 , 48 , 10455-10465).

We have also developed a method to easily synthesize ligands of the compound of Example 1 (Min, J .; Seong, J. E .; Na, S. J .; Cyriac, A .; Lee, B. Y.Bull. Korean Chem . Soc . 2009,30, 745-748).

Of structure 1 which is a high activity catalyst Compounds can be used to economically produce high molecular weight poly (alkylene carbonates). However, poly (alkylene carbonates) by themselves have certain limitations in their development.

The present invention is a poly (alkyl) prepared by alternating copolymerization of carbon dioxide and epoxide by introducing a high molecular compound having a functional group of hydroxy or carboxylic acid into an alternating copolymerization reaction of carbon dioxide / epoxide using a highly developed catalyst. It is an object of the present invention to provide a method for producing a block or graft copolymer of styrene carbonate) and various high molecular compounds and a block or graft copolymer prepared through the method. The block or graft copolymers according to the invention allow for diversification in the use of copolymers of carbon dioxide and epoxides.

In order to achieve the object of the present invention,

By using a complex of the formula (1) as a catalyst,

In the presence of a polymer compound comprising a hydroxyl or carboxylic acid group in the terminal or side chain,

(C2-C20) alkylene oxide unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) ar (C1-C20) aralkyloxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) ar (C1-C20) alkyl (aralkyl) oxy; And (C8 unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6-C20) ar (C1-C20) alkyl (oxyalkyl) or (C1-C20) alkyl -C20) Provides a method for producing a block or graft copolymer of a poly (alkylene carbonate) and the polymer compound comprising the step of alternating copolymerization of carbon dioxide and at least one epoxide compound selected from the group consisting of styrene oxide. .

[Formula 1]

[In Formula 1,

M is cobalt trivalent or chromium trivalent;

A is an oxygen or sulfur atom;

Q is a diradical connecting two nitrogen atoms;

R ¹ To R ¹⁰ is independently of each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;

The R ¹ To R ¹⁰ medium Two may be linked to each other to form a ring;

The R ¹ To At least one of the hydrogens included in R ¹⁰ and Q is a proton group selected from the group consisting of Formula (a), Formula (b) and Formula (c);

X ⁻ is independently of each other a halogen anion; HCO ₃ ^-; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion containing at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylcarbonate anion; (C1-C20) alkylcarbonate anion including at least one of halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C6-C20) arylcarbonate anion; (C6-C20) arylcarbonate anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylamido anion; (C1-C20) alkylamido anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20) arylamido anion; (C6-C20) arylamido anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20) arylcarbamate anion; (C6-C20) arylcarbamate anion comprising one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms;

Z is nitrogen or phosphorus atom;

R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independently of each other (C1-C20) alkyl; (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ²¹ , R ²² and R ²³ or R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ Two of which may be connected to each other to form a ring;

R ⁴¹ , R ⁴² and R ⁴³ are each independently hydrogen; (C1-C20) alkyl; (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ⁴¹ , R ^42, and R ⁴³ may be linked to each other to form a ring;

X 'is an oxygen atom, a sulfur atom or N-R, wherein R is (C1-C20) alkyl;

n is R ¹ To An integer obtained by adding 1 to the total number of protonated groups included in R ¹⁰ and Q;

X ⁻ may coordinate to M;

The nitrogen atom of the imine can be decoordinated to M.]

Carbon dioxide / epoxide copolymerization using the compound of Formula 1 as a catalyst has been patented by the present inventors and also known in the journal (Korean Patent Registration 10-0853358; J. Am . Chem . Soc . 2007, 129 , 8082-8083 Angew . Chem . Int . Ed . , 2008, 47, 7306-7309), copolymerizations performed in the presence of a polymer compound comprising a hydroxyl or carboxylic acid group in the terminal or side chain provided by the present invention are not known. Hydroxyl or carboxyl group in the presence the polymer compound containing a terminal or side-chain polymer chain growth process of the carbon dioxide / epoxide copolymerization of the X containing the said formula (1) type ^{catalysts-coordinated} epoxy to the metal which acts as a Lewis acid Starts by nucleophilic attacking Said. When the polymerization reaction starts, the polymer chain starts to grow from X ^-of the catalyst, and eventually X ^- becomes a polymer chain whose terminal is a carbonate or alkoxy anion. The carbonate or alkoxy anion takes a proton of a hydroxyl or carboxylic acid group having a high molecular compound containing an added hydroxyl or carboxylic acid group in the terminal or side chain, and becomes a compound in the form of an alcohol or a carboxylic acid. The high molecular compound which contains an acidic radical in a terminal or side chain becomes a carboxyl or an alkoxy anion. Once the polymer compound containing a hydroxyl or carboxylic acid group in the terminal or side chain becomes a carbosyl or alkoxy anion, the polymer chain can grow therefrom. The proton exchange reaction is a reaction that can occur fairly quickly, and the resulting polymer material by the proton exchange reaction and the chain growth reaction occurs is the polymer chain grown from X ⁻ included in the initial catalyst and the added hydroxyl or carboxyl. The polymer chain which grew from the high molecular compound containing an acidic radical in a terminal or a side chain is obtained. Since the high molecular compound which contains the injected hydroxyl or carboxylic acid group in a terminal or a side chain is a high molecular compound, the compound obtained by a copolymerization reaction is a block copolymer.

Preferably, in Formula 1, M is cobalt trivalent; A is oxygen; Q is trans-1,2-cyclohexylene, phenylene or ethylene; R ¹ and R ² Are primary (C1-C20) alkyl, identical to or different from each other; R ³ To R ¹⁰ are independently of each other hydrogen or — [YR ⁵¹ _{3 -a} {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ]; Y is C or Si; R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ And R ⁵⁶ are, independently from each other, hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of Group 14 metal substituted with hydrocarbyl, R ⁵⁴ , Two of R ⁵⁵ and R ⁵⁶ may be linked to each other to form a ring; a is an integer from 1 to 3, b is an integer from 1 to 20; n is R ³ To An integer of 4 or more, wherein 1 is added to the total number of quaternary ammonium salts included in R ¹⁰ ; Provided that when a is 1 R ³ To At least three of R ¹⁰ are — [YR ⁵¹ _{3 —a} {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ], and when a is 2 R ³ To At least two of R ¹⁰ are — [YR ⁵¹ _3-a {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ], and when a is 3 R ³ To ^At least one of R ¹⁰ may be used as a catalyst as a complex compound of-[YR ⁵¹ _3-a {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ].

That is, a complex compound represented by the following Chemical Formula 2 may be used as the catalyst.

[Formula 2]

[In the formula (2)

Q is trans-1,2-cyclohexylene, phenylene or ethylene;

R ¹ and R ² Are primary (C1-C20) alkyl, identical to or different from each other;

R ³ To R ¹⁰ are independently of each other hydrogen or — [YR ⁵¹ _{3 -a} {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ];

Y is C or Si;

R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ And R ⁵⁶ are, independently from each other, hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of Group 14 metal substituted with hydrocarbyl, R ⁵⁴ , Two of R ⁵⁵ and R ⁵⁶ may be linked to each other to form a ring;

a is an integer from 1 to 3, b is an integer from 1 to 20;

X ⁻ is independently of each other a halogen anion; HCO ₃ ^-; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion containing at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylcarbonate anion; (C1-C20) alkylcarbonate anion including at least one of halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C6-C20) arylcarbonate anion; (C6-C20) arylcarbonate anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylamido anion; (C1-C20) alkylamido anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20) arylamido anion; (C6-C20) arylamido anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20) arylcarbamate anion; (C6-C20) arylcarbamate anion comprising one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms;

R ³ To The total number of quaternary ammonium salts included by R ¹⁰ is an integer of at least 3;

n is R ³ To The total number of quaternary ammonium salts contained in R ¹⁰ plus 1 is an integer of 4 or more.]

As shown in Formula 2, when R ¹ and R ² are primary alkyl and the number of quaternary ammonium salts included in the compound is 3 or more, a special ligand is formed by forming a unique ligand that is not coordinated with the imine of the structure 1 in a polymerization reaction. Although it was found to show high activity in the carbon dioxide / epoxide copolymerization ( Inorg . Chem . 2009 , 48 , 10455-10465; Bulletin of Korean Chemical Society 2010 , publishing; Korea Patent Application 10-2008-0074435 (2008.07.30) Carbon dioxide / epoxide copolymerization using this type of catalyst and carried out in the presence of a polymer compound containing hydroxyl or carboxylic acid groups in the terminal or side chain is not known.

More preferably, a complex compound represented by the following formula (3) is used as the catalyst.

(3)

[In Formula 3, R ⁶¹ and R ⁶² are each independently methyl or ethyl; X ⁻ are independently of each other a nitrate or acetate anion; The nitrogen of the imine can be coordinating or decoordinating to cobalt, and each anion can also be coordinating to cobalt.]

The complex compound of Chemical Formula 3 is a catalyst that can be easily synthesized in a large amount and is known by the present inventors as the most preferable compound for commercialization ( Bull . Korean Chem . Soc . 2009 , 30 , 745-748). And carbon dioxide / epoxide copolymerization, which is carried out in the presence of a polymer compound containing hydroxyl or carboxylic acid groups in the terminal or side chain, is not known.

The polymer compound including the hydroxyl or carboxylic acid group in the terminal or the side chain is selected from the following Chemical Formulas 4 to 12.

[Formula 4]

R ^70- [OL] _m -OH

[In Formula 4, R ⁷⁰ is (C1-C30) hydrocarbyl or hydrogen with or without an ether group, ester group, or amino group; L is (C 1 -C 30) hydrocarbyl radical; m m in one chain may be the same or different from each other; The number average molecular weight of the polymer compound of formula 4 is 500 to 500000.]

[Chemical Formula 5]

HO ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ H

[Formula 6]

HO- [FO ₂ CE-CO ₂ ] _m -F-OH

[Formula 7]

HO ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -F-OH

[Equation 5 to 7, wherein E is (C1-C30) hydrocarbyl radical, m m in one chain may be the same or different from each other; F is a (C2-C30) hydrocarbyl radical, with or without an ether group, an ester group, or an amino group, and the m Fs in a chain may be the same or different from each other; The number average molecular weight of the polymer compound of Formulas 5 to 7 is 500 to 500000.]

[Formula 8]

{HO- [G-CO ₂ ] _m } _f -R ⁹⁰

[In Formula 8, G is (C1-C15) hydrocarbyl radical; m m in one chain may be the same or different from each other; f is an integer of 1-4, and when f is 1, R ⁹⁰ is hydrogen, (C1-C30) hydrocarbyl, (C1-C30) alkylcarbonyl or (C6-C30) arylcarbonyl, and f is 2 days when R ⁹⁰ is (C1-C30) dihydro car bildayi radical, when f is 3 R ⁹⁰ is (C1-C30) is a hydrocarbyl tree radical, f is R is 4 ^{to 90} is (C1-C30) hydrocarbyl-tetra Radical; The number average molecular weight of the polymer compound of Formula 8 is 500 to 500000.]

[Formula 9]

HO- [Q-OC (O) O] _m -Q-OH

[In Formula 9, Q is independently (C1-C30) hydrocarbyl radical, and m Qs in one chain may be the same or different from each other; The number average molecular weight of the polymer compound of formula 9 is 500 to 500000.]

[Formula 10]

HO-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³

[In Formula 10, R ¹¹¹ and R ¹¹² are independently of each other (C1-C15) hydrocarbyradical; R ¹¹³ is hydrogen or (C1-C30) hydrocarbyl; The number average molecular weight of the polymer compound of formula 10 is 500 to 500000.]

[Formula 11]

R ^100- [T] _m -JH

[Chemical Formula 12]

-{[T] _x- [CH ₂ CR ¹²¹ (JH)] _y } _m-

[In Formulas 11 and 12, T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-, -CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH (Cl) CH = CHCH _2- , and each T belonging to one chain may be the same or different from each other; R ¹⁰⁰ is HJ-, hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy; R ¹²¹ is hydrogen or methyl; J is -O- or -CO _2- ; The number average molecular weight of the high molecular compound of Formula 11 and 12 is 500-50000.

Compound of Formula 4 may be easily prepared by the reaction of Schemes 1 and 2.

Scheme 1

Scheme 2

Although not limited by the molecular weight of the polymer compound to be injected, the molecular weight of the polymer to be added to implement the physical properties of the resulting block copolymer is preferably 500 or more. In addition, when a polymer having a large molecular weight is added, even if a large amount of polymer is added, the number of moles of hydroxyl or carboxyl acid groups contained in the polymer is smaller than that of the anion X ^{− contained in} the catalyst. A polymer chain grown from X ⁻ is obtained and the above object cannot be achieved. The TON that can be implemented as a catalyst having the structure of Chemical Formula 1 is about 50,000. For example, 1 mole (500 Kg) of a polymer having a molecular weight of 500,000 R ⁷⁰ is not hydrogen, 100,000 moles of propylene oxide (5800 Kg) was added, and 1 mole of catalyst (about 1.5 Kg) was added thereto. When polymerizing under carbon dioxide pressure, the maximum amount of polymer that can be obtained is 5000 Kg (equivalent to TON 50000 equivalent, excluding the charged 500 Kg polymer). Among them, the amount of poly (propylene carbonate) grown from the introduced polymer chain is 1/6 of the total amount, and the remainder is the polymer chain grown from X ⁻ . If 5 mole of polymer is added to implement the same activity, the amount of poly (propylene carbonate) grown from the polymer chain and the amount of polymer chain grown from X ⁻ become the same amount. In this calculation, the maximum value of the molecular weight of the polymer capable of preparing the block copolymer is limited to 500,000.

The compounds of Formulas 5 to 7 may be prepared by a condensation reaction of HO ₂ CE-CO ₂ H and HO-F-OH.

The compound of Formula 8 is prepared by the ring-opening polymerization reaction of Scheme 3. Changes in R ⁹⁰ are possible depending on the initiator used.

Scheme 3

The compound of Formula 9 may be prepared by the condensation reaction of dimethyl carbonate or diethyl carbonate and HOQ-OH.

The compound of Formula 10 may be prepared by the ring-opening polymerization reaction of Scheme 4.

Scheme 4

The compound of Formula 11 may be prepared by radical, anion, or cation polymerization of an olefin compound corresponding to each T.

The compound of Formula 12 may be copolymerized with an olefin compound corresponding to each T and CH ₂ = C (Me) (CO ₂ H) or CH ₂ = CH (CO ₂ H) using a suitable initiator or corresponding to each T. Copolymerization of an olefin compound with a CH ₂ = C (Me) (CO ₂ Me), CH ₂ = CH (CO ₂ Me), or CH ₂ = CH (O (O) CMe) compound using a radical or a suitable initiator It can be prepared by hydrolysis. In this case, since the amount of hydroxyl or carboxyl acid groups contained in the introduced polymer is not limited by the molecular weight of the introduced polymer, there is no limitation in the molecular weight of the introduced polymer. It is also not affected by the aspect of the terminal.

In Formula 4, R ⁷⁰ is hydrogen or (C1-C15) alkyl, and L is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-or -CH ₂ CH ₂ CH ₂ CH _2- Do. In Formulas 5 to 7, E is -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , para-phenylene, or 2,6-naphtharenediyl , F is -CH ₂ CH ₂ OCH ₂ CH _2- , -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH ₂ CH _2- , -CH ₂ C (CH ₃ ) _{2 CH 2 -, -CH 2 CH (} CH 3) CH 2 - or _{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 - is preferably a.

In Formula 8, G is -CH _2- , -CH (CH ₃ )-, -CH (CH ₃ ) CH _2- , -CH (CH ₂ CH ₃ ) CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- , and R ⁹⁰ is hydrogen, (C1-C8) alkyl or (C2-C8) alkylcarbonyl.

In Chemical Formula 9, Q is -CH ₂ CH ₂ CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- .

In Formula 10, R ¹¹¹ and R ¹¹² are each independently methyl or phenyl, and R ¹¹³ is preferably hydrogen or (C 1 -C 8) alkyl.

In Formulas 11 and 12, T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-, -CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH (Cl) CH = CHCH ₂ may be selected.

In Formula 11, J is -O-, T is -CH ₂ CH ₂ -or -CH ₂ CH (CH ₂ CH ₃ )-, R ¹⁰⁰ is hydrogen or HO-, J is -CO _2- , T is -CH ₂ CH (C ₆ H ₅ )-, R ¹⁰⁰ is HO ₂ C- or butyl, J is -CO _2- , T is -CH ₂ CH (C ₆ H ₅ ) And R ¹⁰⁰ is HO ₂ C- or butyl can be prepared by anionic polymerizing styrene and terminating the reaction with CO ₂ .

In Chemical Formula 12, T is -CH ₂ CH _2- , -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-or -CH ₂ C (Me) (CO ₂ Me) —, R ¹²¹ is hydrogen or methyl, and J is —CO ₂ —.

The polymer compounds are commonly used polymer compounds that are commercially available from companies such as Aldrich.

Specific examples of the epoxide compound in the above production method include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, Butadiene monoxide, 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycy Diyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxidenorbornene, Limonene oxide, dieldrin, 2,3-epoxidepropylbenzene, styrene oxide, phenylpropylene oxy De, stilbene oxide, chlorostilbene oxide, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl oxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxide Propyl ether, epoxypropyl methoxyphenyl ether, biphenyl glycidyl ether, glycidyl naphthyl ether and the like.

Epoxide compounds may be used for polymerization using an organic solvent as a reaction medium, and examples of the solvent include aliphatic hydrocarbons such as pentane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, chloromethane and methylene chloride. , Chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethylchloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1 It can be used alone or in combination of two or more of halogenated hydrocarbons such as -chloro-2-methylpropane, chlorobenzene and bromobenzene. More preferably, bulk polymerization using the monomer itself as a solvent can be performed.

The molar ratio of epoxide compound to catalyst, ie the epoxide compound: catalyst molar ratio, can be used at 1,000 to 1,000,000, preferably at 50,000 to 200,000. The pressure of carbon dioxide in the copolymerization step may be up to 100 atm at normal pressure, preferably 30 atm at 5 atm. In the copolymerization step, the polymerization temperature may be from 20 ° C to 120 ° C, preferably 50 ° C to 90 ° C.

As a method of polymerizing a poly (alkylene carbonate), it can manufacture by a batch polymerization method, a semi-batch polymerization method, or a continuous polymerization method. In the case of using a batch or semibatch polymerization method, the reaction time may be 0.5 to 24 hours, preferably 0.5 to 4 hours. In the case of using the continuous polymerization method, the average residence time of the catalyst is also preferably 0.5 to 4 hours.

In still another aspect of the present invention, there is provided a method of preparing a block or graft copolymer of a poly (alkylene carbonate) and a polymer compound including hydroxyl or carboxylic acid groups in a terminal or a side chain thereof; And contacting the prepared solution of the block or graft copolymer and the catalyst with a solid inorganic material, a polymer material, or a mixture thereof, which is not dissolved in the solution, thereby preparing a complex of the solid inorganic material or polymer material with the catalyst. It provides a method for producing a poly (alkylene carbonate) comprising; separating the catalyst and the block or graft copolymer prepared by forming.

The method for separating the catalyst after carrying out the carbon dioxide / epoxide copolymerization using the same catalyst has already been known by the present inventors (Korean Patent Application 10-2008-0015454; Angew . Chem . Int . Ed . , 2008 , 47, 7306-7309), a method of separating a catalyst after the copolymerization of a polymer compound containing a hydroxyl or carboxylic acid group selected from Formulas 4 to 12 in a terminal or a side chain is not known.

The solid inorganic material may be a surface-modified or surface-modified silica or alumina, and the polymer material may be a polymer material having a functional group capable of deprotonation reaction by an alkoxy anion, and deprotonation reaction by the alkoxy anion. The functional groups that can occur can be sulfonic acid groups, carboxylic acid groups, phenol groups or alcohol groups. Examples of the solid inorganic material mainly composed of silicon or aluminum including the brester acid point capable of providing protons to the alkoxy anion or the carbonate anion include silica, alumina, aluminosilicate (zeolite), aluminophosphate, Titanium silicate, clay, and the like, and it is more preferable to use silica or alumina which is surface modified or not surface modified.

Preferably, the polymer material is crosslinked with a number average molecular weight of 500 to 10,000,000, although it is possible to dissolve in a solution containing a copolymer and a catalyst even if not crosslinked. More specific examples of "a polymer material having a functional group capable of causing a deprotonation reaction by an alkoxy anion" include a copolymer including a monomer such as Chemical Formulas I to V in the polymer chain, or a homopolymer composed only of such a monomer. It includes. The polymer material acting as such a support may be uncrosslinked as long as it does not dissolve in the above-described solution, but is preferably crosslinked appropriately to reduce solubility.

In another embodiment of the present invention, a block copolymer compound selected from the following Chemical Formulas 13 to 15 is provided. There are no reported examples of block copolymers of such poly (alkylene carbonates) with other polymers.

[Formula 13]

W- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[Wherein, W is R ^70- [OL] _m -O- (Formula d), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d- [OL] _m -O- (Formula e), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O ₂ C- [ E-CO ₂ -FO ₂ C] _m -E-CO _2- (Formula f), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _{d -O- [FO 2 CE-CO} 2] m -FO- ( formula ^{g), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} _{d -O 2 C- [E-CO} 2 -FO 2 C] m -E-CO 2 -FO- ( formula ^{h), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [G-CO ₂ ] _m- (Formula i), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4- CR ^e1 R ^e2 } _d -O- [Q-OC (O) O] _m -QO- (Formula j), -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ (Formula k ), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m- Formula l), R ^100- [T] _m -J- (Formula m) and HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -J- [T] _m -J- (formula n);

R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 can be linked to each other to form a ring, d is an integer from 10 to 5000;

R ⁷⁰ is (C1-C30) hydrocarbyl with or without ether, ester, or amino groups;

L is (C 1 -C 30) hydrocarbyl radical; m m in one chain may be the same or different from each other;

E is (C1-C30) hydrocarbyldi radical and m Es in a chain may be the same or different from each other;

F is a (C2-C30) hydrocarbyl radical, with or without an ether group, an ester group, or an amino group, and the m Fs in a chain may be the same or different from each other; G is (C1-C15) hydrocarbyldi radical and m Gs in one chain may be the same or different from each other;

Q is independently (C 1 -C 30) hydrocarbyl radical; m m in a chain may be the same or different from each other;

R ¹¹¹ and R ¹¹² are independently of each other (C1-C15) hydrocarbyradical; R ¹¹³ is hydrogen or (C1-C30) hydrocarbyl;

J is -O- or -CO _2- ;

T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-,- CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH ( Cl) CH = CHCH ₂ -and the m Ts in one chain may be the same or different from each other;

R ¹⁰⁰ is hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy;

R ^70- [OL] _m -,-[OL] _m- , -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO _2- , -O- [FO of Formulas d to n ₂ CE-CO ₂ ] _m -FO-, -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -FO-, -O- [G-CO ₂ ] _m- , -O -[Q-OC (O) O] _m -QO-, -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ , -O-[(R ¹¹¹ ) (R ¹¹² ) Si- O] _m- , the number average molecular weight of R ^100- [T] _m -J- and -J- [T] _m -J- block is 500 to 500000.]

[Formula 14]

{HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [G-CO ₂ ] _m } _f -R ⁹⁰

[In Formula 14, G is (C1-C15) hydrocarbyl radical; m m in one chain may be the same or different from each other; f is an integer of 1-4, and when f is 1, R ⁹⁰ is hydrogen, (C1-C30) hydrocarbyl, (C1-C30) alkylcarbonyl or (C6-C30) arylcarbonyl, and f is 2 days when R ⁹⁰ is (C1-C30) dihydro car bildayi radical, when f is 3 R ⁹⁰ is (C1-C30) is a hydrocarbyl tree radical, f is R is 4 ^{to 90} is (C1-C30) hydrocarbyl-tetra Radical; The number average molecular weight of-{O- [G-CO ₂ ] _m } _f -R ⁹⁰ blocks is from 500 to 500000, and R ^e1 to R ^e4 are independently of each other hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 5000.]

[Formula 15]

-{[T] _x- [CH ₂ CR ¹²¹ (J- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH)] _y } _m -

[In Formula 15, J is -O- or -CO _2- ; T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-,- CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH ( Cl) CH = CHCH ₂ — and each T in a chain may be the same or different from each other; R ¹²¹ is hydrogen or methyl; The number average molecular weight of the main chain of the polymer is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 50000.]

The maximum turnover number (TON) that can be achieved with the catalyst used in the present invention is about 50000. If d is 5000, the number of grown chains is 10. Five chains grew from the catalyst X ^- and the other five grew from the injected polymer. That is, half is pure poly (alkylene carbonate) and half is considered to be able to impart physical properties of the block copolymer when the block copolymer is obtained.

In Formula 13, when W is R ^70- [OL] _m -O- (Formula d), it is represented by the following Formula 13-d.

[Formula 13-d]

R ^70- [OL] _m -O- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In Formula 13-d, R ⁷⁰ is (C1-C30) hydrocarbyl with or without ether group, ester group, or amino group; L is (C 1 -C 30) hydrocarbyl radical; m m in one chain may be the same or different from each other; The number average molecular weight of R ^70- [OL] _m block is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 5000.]

Specifically, R ⁷⁰ of the polymer compound of Formula 13-d is (C1-C15) alkyl; L is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-or -CH ₂ CH ₂ CH ₂ CH _2- ; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen).

In Formula 13, W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d- [OL] _m -O- (Formula e) In the case represented by the following Chemical Formula 13-e.

[Formula 13-e]

HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d- [OL] _m -O- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In Formula 13-e, L is (C1-C30) hydrocarbyl radical and m of L in one chain may be the same or different from each other; The number average molecular weight of the-[OL] _m block is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 5000.]

Specifically, L of the polymer compound of Formula 13-e is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-or -CH ₂ CH ₂ CH ₂ CH _2- ; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen).

In Chemical Formula 13, W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO _2- (Formula f), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [FO ₂ CE-CO _{2] m} -FO- (formula g) or ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [ E-CO ₂ -FO ₂ C] _m -E-CO ₂ -FO- (formula h) is represented by the following formula 13-f, formula 13-g or formula 13-h.

[Formula 13-f]

HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO _2- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[Formula 13-g]

HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [FO ₂ CE-CO ₂ ] _m -FO- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[Formula 13-h]

HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -FO- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In Formulas 13-f to 13-h, E is (C1-C30) hydrocarbyldi radical and m Es in one chain may be the same or different from each other; F is a (C2-C30) hydrocarbyl radical, with or without an ether group, an ester group, or an amino group, and the m Fs in a chain may be the same or different from each other; -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO _2- , -O- [FO ₂ CE-CO ₂ ] _m -FO-, or -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -FO- block number average molecular weight is 500 to 500000, R ^e1 to R ^e4 are independently of each other hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 5000.]

Specifically E of the polymer compound of the formula 13-g to 13-h is -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , para-phenylene, or 2,6-naphtharendiyl, F is -CH ₂ CH ₂ OCH ₂ CH _2- , -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH ₂ CH ₂ -,- CH ₂ C (CH ₃ ) ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- , R ^e1 to R ^e4 are independently hydrogen Or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units R ^e1 is methyl and the remaining R ^e2 to R ^e4 are all hydrogen May be).

In Chemical Formula 13, W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [G-CO ₂ ] _m- i) is represented by the following formula (13-i).

[Formula 13-i]

HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [G-CO ₂ ] _m- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In Formula 13-i, G is (C1-C15) hydrocarbyldi radical and m Gs in one chain may be the same or different from each other; The number average molecular weight of the -O- [G-CO ₂ ] _m -blocks is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 5000.]

Specifically, G of the polymer compound of Formula 13-i is -CH _2- , -CH (CH ₃ )-, -CH (CH ₃ ) CH _2- , -CH (CH ₂ CH ₃ ) CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen).

In Formula 13, W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [Q-OC (O) O] _m -QO- (Formula j) is represented by the following formula (13-j).

[Formula 13-j]

HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [Q-OC (O) O] _m -QO- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In Formula 13-j, Q is independently (C1-C30) hydrocarbyl radical; m m in one chain may be the same or different from each other; The number average molecular weight of the -O- [Q-OC (O) O] _m -QO- block is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 5000.]

Specifically, Q of the polymer compound of Formula 13-j is -CH ₂ CH ₂ CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen).

In Chemical Formula 13, when W is -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ (Formula k), it is represented by the following Chemical Formula 13-k.

[Formula 13-k]

HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³

[In Formula 13-k, R ¹¹¹ and R ¹¹² are independently of each other (C1-C15) hydrocarbyradical; R ¹¹³ is hydrogen or (C1-C30) hydrocarbyl; The number average molecular weight of the -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ block is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 5000.]

Specifically, R ¹¹¹ and R ¹¹² of the polymer compound of Formula 13-k are each independently methyl or phenyl; R ¹¹³ is hydrogen or (C1-C8) alkyl; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen).

In Formula 13, W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O-[(R ¹¹¹ ) (R ¹¹² ) Si -O] _m- (Formula 1) is represented by the following formula (13-l).

[Formula 13-l]

HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In Chemical Formula 13-1, R ¹¹¹ and R ¹¹² are independently of each other (C1-C15) hydrocarbyradical; The number average molecular weight of the -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -block is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 5000.]

Specifically, R ¹¹¹ and R ¹¹² of the polymer compound of Formula 13-1 are independently of each other methyl or phenyl; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen).

In Formula 13, when W is R ^100- [T] _m -J- (formula m), it is represented by Formula 13-m.

[Formula 13-m]

R ^100- [T] _m -J- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In Formula 13-m, J is -O- or -CO _2- ; T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-,- CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH ( Cl) CH = CHCH ₂ - and the m Ts in one chain may be the same or different from each other; R ¹⁰⁰ is hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy; The number average molecular weight of R ^100- [T] _m -J- block is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 50000.]

T of Formula 13-m is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-, -CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH (Cl) CH = CHCH _2- .

Specifically J of the polymer compound of Formula 13-m is -O-; T is -CH ₂ CH ₂ -or -CH ₂ CH (CH ₂ CH ₃ )-; R ¹⁰⁰ is hydrogen; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen). In addition, J of the polymer compound of Formula 13-m is -CO _2- ; T is -CH ₂ CH (C ₆ H ₅ )-; R ¹⁰⁰ is butyl; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen).

In Formula 13, W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -J- [T] _m -J- (Formula n ) Is represented by the following formula (13-n).

[Formula 13-n]

HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -J- [T] _m -J- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In Formula 13-n, J is -O- or -CO _2- ; T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-,- CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH ( Cl) CH = CHCH ₂ -and the m Ts in one chain may be the same or different from each other; R ¹⁰⁰ is hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy; The number average molecular weight of the -J- [T] _m- J-block is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 50000.]

T of Formula 13-n is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-, -CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH (Cl) CH = CHCH _2- .

Specifically, J of the polymer compound of Formula 13-n is -O-; T is -CH ₂ CH ₂ -or -CH ₂ CH (CH ₂ CH ₃ )-; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen). In addition, J of the polymer compound of Formula 13-n is -CO _2- ; T is -CH ₂ CH (C ₆ H ₅ )-; R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeating units, R ^e1 is methyl And the remaining R ^e2 to R ^e4 may all be hydrogen).

In the polymer compound of Formula 14, G is -CH _2- , -CH (CH ₃ )-, -CH (CH ₃ ) CH _2- , -CH (CH ₂ CH ₃ ) CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- , R ⁹⁰ is hydrogen, (C1-C8) alkyl or (C2-C8) alkylcarbonyl, R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 may be all hydrogen, or R ^e1 to R ^e3 may be all hydrogen and R ^e4 may be methyl (in some repeating units, R ^e1 is methyl and the remaining R ^e2 to R ^e4 are all hydrogen).

In the polymer compound of Formula 15, T is -CH ₂ CH _2- , -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-or -CH ₂ C (Me) (CO ₂ Me) —, R ¹²¹ is hydrogen or methyl, J is —CO ₂ —, R ^e1 to R ^e4 are independently of each other hydrogen or methyl, preferably R ^e1 to R ^e4 May be all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 may be methyl (in some repeating units, R ^e1 is methyl and the remaining R ^e2 to R ^e4 are all hydrogen).

Poly (alkylene carbonate) itself by preparing a block or graft copolymer of a poly (alkylene carbonate) and a polymer compound having a functional group of hydroxy or carboxylic acid with the preparation method according to the present invention. It can diversify its use by supplementing its physical properties. In addition, the obtained block or graft copolymer may be used for the purpose of facilitating blending of poly (alkylene carbonate) and various polymers.

1 is a polystyrene-poly (propylene carbonate) block copolymer GPC curve (Example 13).
2 is polystyrene-poly (propylene carbonate) block copolymer DSC data (Example 13).

The following examples and comparative examples specifically illustrate the effects of the present invention. However, the following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.

Preparation Example 1 Synthesis of Catalyst

The catalyst used in the present invention was prepared as shown below. A compound of the starting material was synthesized by the known methods (Bull. Korean Chem . Soc . 2009 , 30 , 745-748).

compound B Synthesis of

Compound A (100 mg, 0.054 mmol) with AgNO ₃ (37.3 mg, 0.219 mmol) was dissolved in ethanol (3 mL) and stirred overnight. Filtration was carried out using celite to remove the generated AgI. The solvent was removed under reduced pressure in vacuo to yield Compound B in the form of a yellow solid powder (0.80 g, 94%). ¹ H NMR (CDCl ₃ ): δ 3.51 (s, 2H, OH), 8.48 (s, 2H, CH = N), 7.15 (s, 4H, m -H), 3.44 (br, 2H, cyclohexyl-CH) , 3.19 (br, 32H, NCH ₂ ), 2.24 (s, 6H, CH ₃ ), 1.57-1.52 (br, 4H, cyclohexyl-CH ₂ ), 1.43-1.26 (br, 74H), 0.90-070. (br, 36H, CH ₃ ) ppm.

compound C Synthesis of

Compound B (95 mg, 0.061 mmol) and Co (OAc) ₂ (10.7 mg, 0.061 mmol) were added to the flask and methylene chloride (3 mL) was added to dissolve. After stirring under oxygen gas at room temperature for 3 hours, the solvent was removed under reduced pressure to obtain Compound C in the form of a brown solid powder (85 mg, 83%). ¹ H NMR (DMSO-d ₆ , 38 ° C.): major signal set, δ 7.83 (s, 2H, CH = N) 7.27 (br s, 2H, mH), 7.22, 7.19 (brs, 2H, m -H) , 3.88 (br, 1H, cyclohexyl-CH), 3.55 (br, 1H, cyclohexyl-CH), 3.30-2.90 (br, 32H, NCH _{2 )} , 2.58 (s, 3H, CH ₃ ), 2.55 (s, 3H , CH ₃ ), 2.10-1.80 (br, 4H, cyclohexyl-CH ₂ ), 1.70-1.15 (br m, 74H), 1.0-0.80 (br, 36H, CH ₃ ) ppm; Minor signal set, δ 7.65 (s, 2H, CH = N) 7.45 (s, 2H, mH), 7.35 (s, 2H, m -H), 3.60 (br, 2H, cyclohexyl-CH), 3.30-2.90 ( br, 32H, NCH ₂ ), 2.66 (s, 6H, CH ₃ ), 2.10-1.80 (br, 4H, cyclohexyl-CH ₂ ), 1.70-1.15 (br m, 74H), 1.0-0.80 (br, 36H, CH ₃ ) ppm. ¹ H NMR (CD ₂ Cl ₂ ): δ 7.65 (br, 2H, CH = N) 7.34 (br, 2H, mH), 7.16 (br, 2H, m- H), 3.40-2.00 (br, 32H, NCH ₂ ), 2.93 (br s, 6H, CH ₃ ), 2.10-1.80 (br m, 4H, cyclohexyl-CH ₂ ), 1.70-1.15 (br m, 74H), 1.1-0.80 (br, 36H, CH ₃ ) ppm.

Two sets of signals were observed at a ratio of 6: 4 in the ¹ H NMR spectrum obtained by dissolving in DMSO-d ₆ . The major signal set shows that the two phenoxy ligands of the Salen-unit are different, and the minor signal set shows that the two phenoxy ligands are identical. This can be interpreted as compound C in equilibrium as described below in dmso solvent. The presence of substituents with small steric hindrances such as methyl in the ortho-position of the two phenoxy ligands of the salen-unit was found to have a structure in which the imine nitrogen was not coordinated in a polar solvent such as DMSO ( Inorg . Chem . 2009 , 48 , 10455-10465). In methylene chloride, a nonpolar solvent, a broad set of signals was observed. Considering the weak coordination of NO ₃ ^- anion, it is expected that the imine nitrogen coordinates and coordinates decoordination by exchanging nitrate anion and acetate anion on the two axial coordination surfaces as shown below. .

<Expected Structure of DMSO of Compound C >

<화합물 C의 CH₂Cl₂에서의 예상 구조>

<Expected Structure of CH ₂ Cl ₂ of Compound C >

Example 1 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (ethylene Glycol)

Copolymerization reaction

Compound C (3.0 mg, monomer / catalyst = 100,000) and propylene oxide (10.0 g, 172 mmol) prepared in Preparation Example 1 were added to a 50 mL bomb reactor, and poly (ethylene glycol) ( R ⁷⁰ of Formula 4 is hydrogen, L is -CH ₂ CH _2- , Mn is 8500-11500, 200 mg, [OH] / [Co] = 22) and then the reactor was assembled. After applying a pressure of 15 bar of carbon dioxide gas, the reactor was immersed in an oil bath previously adjusted to 73 ° C. and stirring started. After 35 minutes the reactor internal temperature reached 70 ° C. and from this point the decrease in reactor pressure was observed. The polymerization reaction was carried out for 1 hour from the time when the reaction was started at the reactor internal temperature reached 70 ℃. The reactor was immersed in a cold bath, cooled and terminated by removing carbon dioxide gas. A light yellow, viscous solution was obtained.

Catalytic separation

10 g of propylene oxide was further added to the prepared viscous solution to lower the viscosity of the solution, followed by silica gel (400 mg, manufactured by Merck, 0.040-0.063 mm particle size (230-400 mesh) pad, and a colorless solution. The monomers were removed by vacuum depressurization, in which case 1-10% of propylene carbonate by-products were produced, The resulting by-product propylene carbonate was removed by storing the sample overnight in a vacuum oven at 150 ° C. 1.65 g of pure A polymer was obtained, which had a TON value of 7600 and a polystyrene as standard, the molecular weight (Mn) measured at GPC was 68300 and the molecular weight distribution (Mw / Mn) was 1.48. The nitrate or acetate possessed by the catalyst in the GPC curve The polymer chains grown at were found in the vicinity of 47000 and the growths at the injected polymer chains were relatively widely distributed at 105000. The glass transition temperature (Tg) measured in DSC was 26 ° C. In the ¹ H NMR spectrum, the poly (propylene carbonate) signal was seen at 5.01, 4.32-4.10, and 1.36 ppm, and the injected poly (ethylene glycol) signal was 3.66. Observed at ppm.

200 mg ([OH] / [Co] = 108) of a polymer having a Mn of 1950-2050 was added thereto, and polymerization was carried out in the same manner to obtain 2.44 g of a block copolymer (TOF, 12200 h ⁻¹ ). Mn of the obtained polymer was 19900 and a molecular weight distribution (Mw / Mn) was 1.30. A glass transition signal was observed at -27 ° C in the DSC.

250 mg ([OH] / [Co] = 8) of a polymer having a Mn of 35000 was added instead, and polymerization was performed in the same manner to obtain 3.01 g of a block copolymer (TOF, 15100 h ⁻¹ ). Mn of the obtained polymer was 111000 and a molecular weight distribution (Mw / Mn) was 1.57. A glass transition signal was observed at 39 ° C. in the DSC and a melting signal was observed at 53 ° C. further.

500 mg ([OH] / [Co] = 16) of a polymer having a Mn of 35000 was added thereto, and polymerization was performed in the same manner to obtain 2.17 g of a block copolymer (TOF, 9100 h ⁻¹ ). Mn of the obtained polymer was 54900 and a molecular weight distribution (Mw / Mn) was 1.19. A glass transition signal was observed at 27 ° C. in the DSC and a melting signal was observed at 55 ° C. further.

Example 2 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (propylene Glycol)

Poly (propylene glycol) instead of poly (ethylene glycol) (R ⁷⁰ in formula 4 is hydrogen, L is —CH ₂ CH (CH ₃ ) —, Mn is 3500, 350 mg, [OH] / [Co] = 112) Was added to carry out the polymerization reaction in the same manner as in Example 1, and the catalyst was removed by the same method. 2.82 g of pure polymer was obtained, which had a TON value of 13600 and a molecular weight (Mn) of 22800 and a molecular weight distribution (Mw / Mn) of 1.27 measured in GPC using polystyrene as a standard. The glass transition temperature (Tg) measured in DSC was 36 ° C. ^The poly (propylene glycol) signal injected in the ¹ H NMR spectrum was seen at 3.55, 3.42 and 1.56 ppm.

Example 3 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation Using Poly (tetrahydrofuran)

Poly (tetrahydrofuran) instead of poly (ethylene glycol) (R ⁷⁰ in formula 4 is hydrogen, L is —CH ₂ CH ₂ CH ₂ CH ₂ —, Mn is 2900, 260 mg, [OH] / [Co] = 100) was added to carry out the polymerization reaction in the same manner as in Example 1, and the catalyst was removed by the same method. 3.13 g of pure polymer was obtained, which had a TON value of 15700, had a molecular weight (Mn) of 33800 and a molecular weight distribution (Mw / Mn) of 1.13 measured in GPC using polystyrene as a standard. Large growths were observed at 28100 in the polymer chain injected from the GPC curve. The glass transition temperature (Tg) measured in DSC was 37 ° C. ^The poly (tetrahydrofuran) signal injected in the ¹ H NMR spectrum was observed at 3.42 and 1.64 ppm.

Example 4 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (di (ethylene glycol) adipic Acid)) (poly (di (ethylene glycol) adipate))

Poly (di (ethylene glycol) adipic acid instead of poly (ethylene glycol) (E in Formula 5-7 is -CH ₂ CH ₂ CH ₂ CH _2- , F is -CH ₂ CH ₂ OCH ₂ CH _2- , Mn is 2500, 200 mg, [OH] / [Co] = 90) was added to carry out the polymerization reaction in the same manner as in Example 1. The catalyst was removed by the same method, and 2.18 g of pure polymer was obtained, which gave a TON value. The molecular weight (Mn) measured in GPC was 45200 and the molecular weight distribution (Mw / Mn) was 1.09, corresponding to 11900. The glass transition temperature (Tg) measured in DSC was 35 ° C. ¹ H NMR Poly (di (ethylene glycol) adipic acid) signals injected in the spectra were observed at 3.71, 2.38 and 1.68 ppm.

Example 5 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (3-hydroxybutyric Acid)

Instead of poly (ethylene glycol), poly (3-hydroxybutanoic acid) (G in Formula 8 is -CH (CH ₃ ) CH _2- , f is 1, R ⁹⁰ is hydrogen, 200 mg) is added to Example 1 The polymerization was carried out in the same manner as in the following and the catalyst was removed by the same method. 1.27 g of pure polymer was obtained, which had a TON value of 6900 and a molecular weight (Mn) of 107100 and a molecular weight distribution (Mw / Mn) of 1.32 measured in GPC using polystyrene as a standard. On the GPC curves, polymer chains grown on nitrates or acetates possessed by the catalyst were seen around 84600, and growth on the polymer chains injected was observed in 199500. The glass transition temperature (Tg) measured in DSC was 25 ° C. The methyl signal of the poly (3-hydroxybutanoic acid) injected in the ¹ H NMR spectrum was observed at 1.30 ppm, and the remaining signals were not observed broadly.

Example 6 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (caprolactone diol)

Poly (caprolactone diol) instead of poly (ethylene glycol) (G in Formula 8 is -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- , f is 2, aldrich, Mn is 2000, 250 mg, [OH] / [Co] = 139) was added to the polymerization reaction in the same manner as in Example 1 and the catalyst was removed by the same method. 3.29 g of pure polymer was obtained, which had a TON value of 15900 and had a molecular weight (Mn) of 32000 and a molecular weight distribution (Mw / Mn) of 1.07 as measured by GPC using polystyrene as a standard. The glass transition temperature (Tg) measured in DSC was 33 ° C. ^The poly (caprolactone diol) signal injected in the ¹ H NMR spectrum was observed at 4.07, 2.33, and 1.68 ppm.

Example 7 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (caprolactone triol)

Poly (caprolactone triol) instead of poly (ethylene glycol) (G in Formula 8 is -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- , f is 3, R ⁹⁰ is CH ₃ CH ₂ C {CH _2- } ₃ , Mn was 900, 200 mg, [OH] / [Co] = 374) was added to the polymerization reaction in the same manner as in Example 1 and the catalyst was removed by the same method. 1.21 g of pure polymer was obtained, which had a TON value of 6600, had a molecular weight (Mn) of 8300 and a molecular weight distribution (Mw / Mn) of 1.04 as measured by GPC using polystyrene as a standard. The glass transition temperature (Tg) measured in DSC was 20 ° C. Poly (caprolactone triol) signals injected in the ¹ H NMR spectrum were observed at 3.99, 2.33, 1.67, and 1.23 ppm.

Example 8 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (hexamethylene Carbonate) Diol

Poly (hexamethylene carbonate) diol instead of poly (ethylene glycol) (Q in Formula 9 is -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- , Mn is 2000, 200 mg, [OH] / [Co] = 112) was added to the polymerization reaction in the same manner as in Example 1 and the catalyst was removed by the same method. 2.18 g of pure polymer was obtained, which had a TON value of 11900 and had a polystyrene as standard, the molecular weight (Mn) measured at GPC was 24000, and the molecular weight distribution (Mw / Mn) was 1.07. The glass transition temperature (Tg) measured in DSC was 31 ° C. ^The poly (hexamethylene carbonate) diol signal injected in the ¹ H NMR spectrum was observed at 3.67, 1.70, and 1.43 ppm.

Example 9 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (dimethylsiloxane)

Poly (dimethylsiloxane) instead of poly (ethylene glycol) (R ^{111 in} Formula 10, R ¹¹² is methyl, R ¹¹³ is hydrogen, Viscosity 1,800-2,200 cSt, 200 mg) was added to the polymerization reaction in the same manner as in Example 1 and the catalyst was removed by the same method. 1.90 g of pure polymer was obtained, which had a TON value of 10000 and had a polystyrene as standard, and the molecular weight (Mn) measured in GPC was 148000 and the molecular weight distribution (Mw / Mn) was 1.39. The glass transition temperature (Tg) measured in DSC was 42 ° C. Poly (dimethylsiloxane) signal injected in the ¹ H NMR spectrum was observed at 0.09 ppm.

Example 10 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Polyethylene Monoalcohol

Polyethylene monoalcohol instead of poly (ethylene glycol) (J in formula 11 is -O-, T is -CH ₂ CH _2- , R ¹⁰⁰ is hydrogen, Mn is 700, 100 mg, [OH] / [Co] = 80 ) Was added to the polymerization reaction in the same manner as in Example 1, and the catalyst was removed by the same method. 1.80 g of pure polymer was obtained, which had a TON value of 9900 and had a molecular weight (Mn) of 18800 and a molecular weight distribution (Mw / Mn) of 1.18 as measured by GPC using polystyrene as a standard. The glass transition temperature (Tg) of poly (propylene carbonate) was observed at 37.2 ° C. and the melting (Tm) signal of PE was observed at 92 ° C. in the DSC curve. Polyethylene signals injected in the ¹ H NMR spectrum were observed at 1.27 ppm.

500 mg ([OH] / [Co] = 397) of the same polyethylene alcohol was added instead, and polymerization was carried out in the same manner to obtain 2.94 g of a block copolymer (TOF, 13500 h ⁻¹ ). Mn of the obtained polymer was 7800 and a molecular weight distribution (Mw / Mn) was 1.18. A glass transition signal was observed at 34 ° C. in the DSC and a melting signal was observed at 96 ° C. further.

1.00 g ([OH] / [Co] = 794) of the same polyethylene alcohol was added instead, and polymerization was carried out in the same manner to obtain 2.56 g of a block copolymer (TOF, 8600 h ⁻¹ ). Mn of the obtained polymer was 3500 and a molecular weight distribution (Mw / Mn) was 1.45. A glass transition signal was observed at 26 ° C. in the DSC and a melting signal was observed at 103 ° C. further.

Example 11 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (ethylene-co-acrylic Acid)

Poly (ethylene-co-acrylic acid) instead of poly (ethylene glycol) (T in formula 12 is -CH ₂ CH _2- , R ¹²¹ is hydrogen, J is -CO _2- , Brookfield viscosity 575 cps (145 ° C), 100 mg, 5 wt% acrylic acid, [COOH] / [Co] = 39) was added to carry out the polymerization in the same manner as in Example 1, and the catalyst was removed by the same method. 2.23 g of pure polymer was obtained, which had a TON value of 12200 and had a polystyrene as standard and a molecular weight (Mn) measured at GPC was 64500 and a molecular weight distribution (Mw / Mn) was 2.01. In the GPC curve, the polymer chains grown in the nitrate or acetate of the catalyst were observed to be small at around 30000, the chains grown in the water were observed to be small at around 63000, and the growths in the injected polymer chains were distributed relatively wide at 106900. Was observed. The glass transition temperature (Tg) of poly (propylene carbonate) in the DSC curve was observed at 38.9 ° C, and the melting (Tm) signal of PE was observed at 65 ° C and 95 ° C. ^The poly (ethylene-co-acrylic acid) signal injected in the ¹ H NMR spectrum was observed at 1.27 ppm.

200 mg ([OH] / [Co] = 78) of the same poly (ethylene-co-acrylic acid) was added instead and subjected to polymerization in the same manner to obtain 2.00 g of a block copolymer (TOF, 10700 h ^-1 ). . Mn of the obtained polymer was 37900 and a molecular weight distribution (Mw / Mn) was 1.79. A glass transition signal was observed at 37 ° C. in the DSC and a melting signal was observed at 98 ° C. further.

400 mg ([OH] / [Co] = 154) of the same poly (ethylene-co-acrylic acid) were added instead and subjected to polymerization in the same manner to obtain 2.86 g of a block copolymer (TOF, 13800 h ^-1 ) . Mn of the obtained polymer was 34000 and a molecular weight distribution (Mw / Mn) was 1.54. A glass transition signal was observed at 36 ° C. in the DSC and a melting signal was observed at 102 ° C. further.

600 mg ([OH] / [Co] = 231) of the same poly (ethylene-co-acrylic acid) were added instead and subjected to polymerization in the same manner to obtain 2.73 g of a block copolymer (TOF, 11500 h ⁻¹ ) . Mn of the obtained polymer was 22500 and a molecular weight distribution (Mw / Mn) was 1.58. A glass transition signal was observed at 33 ° C. in the DSC and a melting signal was observed at 102 ° C. further.

Example 12 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Poly (methyl Methacrylate- co -Methacrylic Acid)

Poly (methyl methacrylate- co -methacrylic acid) instead of poly (ethylene glycol) (T in formula 12 is -CH ₂ C (Me) (CO ₂ Me)-, R ¹²¹ is methyl, J is -CO ₂ -, x: y = 1: 0.016, Mn 15,000, 200 mg, [COOH] / [Co] = 18) was added to the polymerization reaction in the same manner as in Example 1 and the catalyst was removed by the same method . 2.06 g of pure polymer was obtained, which had a TON value of 11200 and a molecular weight (Mn) of 118500 and a molecular weight distribution (Mw / Mn) of 2.23 measured in GPC using polystyrene as a standard. In the GPC curve, the polymer chains grown on nitrate or acetate of the catalyst were observed around 55400, the chains grown on water were observed around 115400, and the growths on the injected polymer chains were largely distributed at 483500. . The glass transition temperature (Tg) measured in DSC was 37 ° C. Poly (methyl methacrylate- co -methacrylic acid) signals injected in the ¹ H NMR spectrum were observed at 3.62, 1.04 and 0.86 ppm.

400 mg ([OH] / [Co] = 36) of the same poly (methyl methacrylate- co -methacrylic acid) was added instead and polymerization was carried out in the same manner to obtain 1.94 g of a block copolymer (TOF, 8500 h ^-1 ). Mn of the obtained polymer was 71000 and a molecular weight distribution (Mw / Mn) was 1.93. A glass transition signal was observed at 34 ° C. in the DSC.

Example 13 Carbon Dioxide / Propylene Oxide Copolymerization and Catalyst Separation in the Presence of Polystyrene Carboxylic Acid

Polystyrene carboxylic acid instead of poly (ethylene glycol) (J in formula 11 is -C (O) O-, T is -CH ₂ CH (Ph)-, R ¹⁰⁰ is butyl, Mn is 44000, 250 mg, [OH] / [Co] = 3) was added to the polymerization reaction in the same manner as in Example 1 and the catalyst was removed by the same method. 2.34 g of pure polymer was obtained, which had a TON value of 11500, had a molecular weight (Mn) of 123000 and a molecular weight distribution (Mw / Mn) of 1.43 measured in GPC using polystyrene as a standard. In the DSC curve, the glass transition temperature (Tg) of poly (propylene carbonate) was observed at 41 ° C, and the glass transition temperature (Tg) of polystyrene was weakly observed at 107 ° C. Polystyrene signals injected in the ¹ H NMR spectrum were observed broadly at 7.20-6.40.

500 mg ([OH] / [Co] = 6) of the same polystyrene carboxylic acid were added instead, and polymerization was carried out in the same manner to obtain 2.50 g of block copolymer (TOF, 9700 h ⁻¹ ). Mn of the obtained polymer was 113500 and a molecular weight distribution (Mw / Mn) was 1.50 (FIG. 1). A glass transition signal was observed at 43 ° C. in the DSC and a glass transition signal was further observed at 108 ° C. (FIG. 2).

Claims (31)

By using a complex of the formula (1) as a catalyst,
In the presence of a polymer compound comprising a hydroxyl or carboxylic acid group in the terminal or side chain,
(C2-C20) alkylene oxide unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) ar (C1-C20) aralkyloxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) ar (C1-C20) alkyl (aralkyl) oxy; And (C8 unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6-C20) ar (C1-C20) alkyl (oxyalkyl) or (C1-C20) alkyl -C20) A method of preparing a block or graft copolymer of poly (alkylene carbonate) and the high molecular compound comprising alternating copolymerization of at least one epoxide compound and carbon dioxide selected from the group consisting of styrene oxide.
[Formula 1]

[In the above formula (1)
M is cobalt trivalent or chromium trivalent;
A is an oxygen or sulfur atom;
Q is a diradical connecting two nitrogen atoms;
R ¹ To R ¹⁰ is independently of each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;
The R ¹ To R ¹⁰ medium Two may be linked to each other to form a ring;
The R ¹ To At least one of the hydrogens included in R ¹⁰ and Q is a proton group selected from the group consisting of Formula (a), Formula (b) and Formula (c);

X ⁻ is independently of each other a halogen anion; HCO ₃ ^-; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^-; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion containing at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylcarbonate anion; (C1-C20) alkylcarbonate anion including at least one of halogen atom, nitrogen atom, oxygen atom, silicon atom, sulfur atom and phosphorus atom; (C6-C20) arylcarbonate anion; (C6-C20) arylcarbonate anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylamido anion; (C1-C20) alkylamido anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20) arylamido anion; (C6-C20) arylamido anion including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; (C6-C20) arylcarbamate anion; (C6-C20) arylcarbamate anion comprising one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms;
Z is nitrogen or phosphorus atom;
R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independently of each other (C1-C20) alkyl; (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ²¹ , R ²² and R ²³ or R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ Two of which may be connected to each other to form a ring;
R ⁴¹ , R ⁴² and R ⁴³ are each independently hydrogen; (C1-C20) alkyl; (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ⁴¹ , R ^42, and R ⁴³ may be linked to each other to form a ring;
X 'is an oxygen atom, a sulfur atom or NR where R is (C1-C20) alkyl;
n is R ¹ To An integer obtained by adding 1 to the total number of protonated groups included in R ¹⁰ and Q;
X ⁻ may coordinate to M;
The nitrogen atom of the imine can be decoordinated to M.] The method of claim 1,
M is cobalt trivalent;
A is oxygen;
Q is trans-1,2-cyclohexylene, phenylene or ethylene;
R ¹ and R ² Are primary (C1-C20) alkyl, identical to or different from each other;
R ³ To R ¹⁰ are independently of each other hydrogen or — [YR ⁵¹ _{3 -a} {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ];
Y is C or Si;
R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ And R ⁵⁶ are, independently from each other, hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl including one or more of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of Group 14 metal substituted with hydrocarbyl, R ⁵⁴ , Two of R ⁵⁵ and R ⁵⁶ may be linked to each other to form a ring;
a is an integer from 1 to 3, b is an integer from 1 to 20;
n is R ³ To An integer of 4 or more, wherein 1 is added to the total number of quaternary ammonium salts included in R ¹⁰ ;
Provided that when a is 1 R ³ To At least three of R ¹⁰ are — [YR ⁵¹ _{3 —a} {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ], and when a is 2 R ³ To At least two of R ¹⁰ are — [YR ⁵¹ _3-a {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ], and when a is 3 R ³ To ^At least one of R ¹⁰ is-[YR ⁵¹ _3-a {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ]. The method of claim 2,
Method for producing a complex of the formula (3) as the catalyst.
(3)

[In Formula 3, R ⁶¹ and R ⁶² are each independently methyl or ethyl; X ⁻ are independently of each other a nitrate or acetate anion; The nitrogen of the imine can be coordinating or decoordinating to cobalt, and each anion can also be coordinating to cobalt.] The method of claim 1,
The polymer compound including the hydroxyl or carboxylic acid group in the terminal or the side chain is selected from the following formula (4) to (12).
[Chemical Formula 4]
R ^70- [OL] _m -OH
[In Formula 4, R ⁷⁰ is (C1-C30) hydrocarbyl or hydrogen with or without an ether group, ester group, or amino group; L is (C 1 -C 30) hydrocarbyl radical; m m in one chain may be the same or different from each other; The number average molecular weight of the polymer compound of formula 4 is 500 to 500000.]

[Chemical Formula 5]
HO ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ H
[Formula 6]
HO- [FO ₂ CE-CO ₂ ] _m -F-OH
[Formula 7]
HO ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -F-OH
[Equation 5 to 7, wherein E is (C1-C30) hydrocarbyl radical, m m in one chain may be the same or different from each other; F is a (C2-C30) hydrocarbyl radical, with or without an ether group, an ester group, or an amino group, and the m Fs in a chain may be the same or different from each other; The number average molecular weight of the polymer compound of Formulas 5 to 7 is 500 to 500000.]

[Chemical Formula 8]
{HO- [G-CO ₂ ] _m } _f -R ⁹⁰
[In Formula 8, G is (C1-C15) hydrocarbyl radical; m m in one chain may be the same or different from each other; f is an integer of 1-4, and when f is 1, R ⁹⁰ is hydrogen, (C1-C30) hydrocarbyl, (C1-C30) alkylcarbonyl or (C6-C30) arylcarbonyl, and f is 2 days when R ⁹⁰ is (C1-C30) dihydro car bildayi radical, when f is 3 R ⁹⁰ is (C1-C30) is a hydrocarbyl tree radical, f is R is 4 ^{to 90} is (C1-C30) hydrocarbyl-tetra Radical; The number average molecular weight of the polymer compound of Formula 8 is 500 to 500000.]

[Formula 9]
HO- [Q-OC (O) O] _m -Q-OH
[In Formula 9, Q is independently (C1-C30) hydrocarbyl radical, and m Qs in one chain may be the same or different from each other; The number average molecular weight of the polymer compound of formula 9 is 500 to 500000.]

[Formula 10]
HO-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³
[In Formula 10, R ¹¹¹ and R ¹¹² are independently of each other (C1-C15) hydrocarbyradical; R ¹¹³ is hydrogen or (C1-C30) hydrocarbyl; The number average molecular weight of the polymer compound of formula 10 is 500 to 500000.]

(11)
R ^100- [T] _m -JH
[Formula 12]
-{[T] _x- [CH ₂ CR ¹²¹ (JH)] _y } _m-
[In Formulas 11 and 12, T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-, -CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH Each T in = CHCH ₂ -or -CH (Cl) CH = CHCH ₂ - and in one chain may be the same or different from each other; R ¹⁰⁰ is HJ-, hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy; R ¹²¹ is hydrogen or methyl; J is -O- or -CO _2- ; The number average molecular weight of the polymer compounds of the formulas (11) and (12) is 500 to 500000.] The method of claim 4, wherein
R ⁷⁰ is hydrogen or (C 1 -C 15) alkyl, and L is —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, or —CH ₂ CH ₂ CH ₂ CH ₂ —. The method of claim 4, wherein
E is -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , para-phenylene, or 2,6-naphtharendiyl, F is -CH ₂ CH ₂ OCH ₂ CH _2- , -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH ₂ CH _2- , -CH ₂ C (CH ₃ ) ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ — or —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —. The method of claim 4, wherein
G is -CH _2- , -CH (CH ₃ )-, -CH (CH ₃ ) CH _2- , -CH (CH ₂ CH ₃ ) CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- And R ⁹⁰ is hydrogen, (C1-C8) alkyl or (C2-C8) alkylcarbonyl. The method of claim 4, wherein
Q is -CH ₂ CH ₂ CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- . The method of claim 4, wherein
R ¹¹¹ and R ¹¹² are each independently methyl or phenyl, and R ¹¹³ is hydrogen or (C 1 -C 8) alkyl. The method of claim 4, wherein
T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-, -CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH (Cl) CH = CHCH _2- . The method of claim 10,
Wherein J is -O-, T is -CH ₂ CH ₂ -or -CH ₂ CH (CH ₂ CH ₃ )-, and R ¹⁰⁰ is hydrogen or HO-. The method of claim 10,
J is -CO _2- , T is -CH ₂ CH (C ₆ H ₅ )-, and R ¹⁰⁰ is HO ₂ C- or butyl. The method of claim 4, wherein
T is —CH ₂ CH ₂ —, —CH ₂ CH (C ₆ H ₅ ) —, —CH ₂ CH (CO ₂ Me) —, —CH ₂ CH (Cl) — or —CH ₂ C (Me) ( CO ₂ Me) —, R ¹²¹ is hydrogen or methyl, and J is —CO ₂ —. 15. A method according to any one of claims 1 to 13, comprising the steps of preparing a block or graft copolymer of a poly (alkylene carbonate) and a polymer compound comprising a hydroxyl or carboxylic acid group in a terminal or side chain; And
A solution in which the prepared block or graft copolymer and the catalyst are dissolved is contacted with a solid inorganic material, a polymer material, or a mixture thereof, which is not dissolved in the solution to form a complex of the solid inorganic material or polymer material and the catalyst. Separating the block or graft copolymer and the catalyst by the preparation; poly (alkylene carbonate) comprising a. The method of claim 14,
The inorganic material of the solid phase is a surface-modified or unmodified silica or alumina, and the poly (alkylene carbonate) is characterized in that the polymer material of the solid phase is a polymer material having a functional group capable of deprotonation reaction by an alkoxy anion. Method of manufacture). 16. The method of claim 15,
Method for producing a poly (alkylene carbonate), characterized in that the functional group capable of deprotonation reaction by the alkoxy anion is a sulfonic acid group, carboxylic acid group, phenol group or alcohol group. A block copolymer compound selected from the formulas (13) to (15).
[Formula 13]
W- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH
[Wherein, W is R ^70- [OL] _m -O- (Formula d), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d- [OL] _m -O- (Formula e), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O ₂ C- [ E-CO ₂ -FO ₂ C] _m -E-CO _2- (Formula f), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _{d -O- [FO 2 CE-CO} 2] m -FO- ( formula ^{g), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} _{d -O 2 C- [E-CO} 2 -FO 2 C] m -E-CO 2 -FO- ( formula ^{h), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [G-CO ₂ ] _m- (Formula i), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4- CR ^e1 R ^e2 } _d -O- [Q-OC (O) O] _m -QO- (Formula j), -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ (Formula k ), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m- Formula l), R ^100- [T] _m -J- (Formula m) and HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -J- [T] _m -J- (formula n);
R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 can be linked to each other to form a ring, d is an integer from 10 to 5000;
R ⁷⁰ is (C1-C30) hydrocarbyl with or without ether, ester, or amino groups;
L is (C 1 -C 30) hydrocarbyl radical; m m in one chain may be the same or different from each other;
E is (C1-C30) hydrocarbyldi radical and m Es in a chain may be the same or different from each other;
F is a (C2-C30) hydrocarbyl radical, with or without an ether group, an ester group, or an amino group, and the m Fs in a chain may be the same or different from each other; G is (C1-C15) hydrocarbyldi radical and m Gs in one chain may be the same or different from each other;
Q is independently (C 1 -C 30) hydrocarbyl radical; m m in a chain may be the same or different from each other;
R ¹¹¹ and R ¹¹² are independently of each other (C1-C15) hydrocarbyradical; R ¹¹³ is hydrogen or (C1-C30) hydrocarbyl;
J is -O- or -CO _2- ;
T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-,- CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH ( Cl) CH = CHCH ₂ -and the m Ts in one chain may be the same or different from each other;
R ¹⁰⁰ is hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy;
R ^70- [OL] _m -,-[OL] _m- , -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO _2- , -O- [FO of Formulas d to n ₂ CE-CO ₂ ] _m -FO-, -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -FO-, -O- [G-CO ₂ ] _m- , -O -[Q-OC (O) O] _m -QO-, -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ , -O-[(R ¹¹¹ ) (R ¹¹² ) Si- O] _m- , the number average molecular weight of R ^100- [T] _m -J- and -J- [T] _m -J- block is 500 to 500000.]

[Formula 14]
{HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [G-CO ₂ ] _m } _f -R ⁹⁰
[In Formula 14, G is (C1-C15) hydrocarbyl radical; m m in one chain may be the same or different from each other; f is an integer of 1-4, and when f is 1, R ⁹⁰ is hydrogen, (C1-C30) hydrocarbyl, (C1-C30) alkylcarbonyl or (C6-C30) arylcarbonyl, and f is 2 days when R ⁹⁰ is (C1-C30) dihydro car bildayi radical, when f is 3 R ⁹⁰ is (C1-C30) is a hydrocarbyl tree radical, f is R is 4 ^{to 90} is (C1-C30) hydrocarbyl-tetra Radical; The number average molecular weight of-{O- [G-CO ₂ ] _m } _f -R ⁹⁰ blocks is from 500 to 500000, and R ^e1 to R ^e4 are independently of each other hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 5000.]

[Formula 15]
-{[T] _x- [CH ₂ CR ¹²¹ (J- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH)] _y } _m -
[In Formula 15, J is -O- or -CO _2- ; T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-,- CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH ( Cl) CH = CHCH ₂ — and each T in a chain may be the same or different from each other; R ¹²¹ is hydrogen or methyl; The number average molecular weight of the main chain is 500 to 500000, and R ^e1 to R ^e4 are each independently hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted with halogen or (C1-C20) alkoxy, R ^e1 to R ^e4 may be linked to each other to form a ring, and d is an integer from 10 to 50000.] The method of claim 17,
W is R ^70- [OL] _m -O- (Formula d); R ⁷⁰ is (C1-C15) alkyl; L is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-or -CH ₂ CH ₂ CH ₂ CH _2- ; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d- [OL] _m -O- (Formula e); L is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-or -CH ₂ CH ₂ CH ₂ CH _2- ; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O ₂ C- [E-CO ₂ -FO ₂ C] _m- E-CO _2- (Formula f), HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [FO ₂ CE-CO ₂ ] _m -FO- (formula g) or ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [E-CO 2 -FO ₂ C] _m -E-CO ₂ -FO- (formula h); E is -CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , para-phenylene, or 2,6-naphtharenediyl; F is -CH ₂ CH ₂ OCH ₂ CH _2- , -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH ₂ CH _2- , -CH ₂ C (CH ₃ ) ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [G-CO ₂ ] _m- (Formula i); G is -CH _2- , -CH (CH ₃ )-, -CH (CH ₃ ) CH _2- , -CH (CH ₂ CH ₃ ) CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [Q-OC (O) O] _m -QO- ( Formula j); Q is -CH ₂ CH ₂ CH ₂ CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
W is -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ (formula k); R ¹¹¹ and R ¹¹² are independently of each other methyl or phenyl; R ¹¹³ is hydrogen or (C1-C8) alkyl; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O-[(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -(Formula 1); R ¹¹¹ and R ¹¹² are independently of each other methyl or phenyl; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
T is -CH ₂ CH _2- , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-, -CH ₂ C (Me) (CO ₂ Me)-, -CH ₂ CH (OC (O) CH ₃ )-, -CH ₂ CH = CHCH _2- , -CH (Me) CH = CHCH ₂ -or -CH (Cl) CH = CHCH ₂ -wherein the block copolymer compound. The method of claim 17,
W is R ^100- [T] _m -J- (formula m); J is -O-; T is -CH ₂ CH ₂ -or -CH ₂ CH (CH ₂ CH ₃ )-; R ¹⁰⁰ is hydrogen; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
W is R ^100- [T] _m -J- (formula m); J is -CO _2- ; T is -CH ₂ CH (C ₆ H ₅ )-; R ¹⁰⁰ is butyl; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -J- [T] _m -J- (Formula n); J is -O-; T is -CH ₂ CH ₂ -or -CH ₂ CH (CH ₂ CH ₃ )-; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
W is HO-CR ^e3 R ^e4 -CR ^e1 R ^e2- {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -J- [T] _m -J- (Formula n); J is -CO _2- ; T is -CH ₂ CH (C ₆ H ₅ )-; R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound. The method of claim 17,
In Formula 14, G is -CH _2- , -CH (CH ₃ )-, -CH (CH ₃ ) CH _2- , -CH (CH ₂ CH ₃ ) CH ₂ -or -CH ₂ CH ₂ CH ₂ CH ₂ CH _2- , R ⁹⁰ is hydrogen, (C1-C8) alkyl or (C2-C8) alkylcarbonyl, and R ^e1 to R ^e4 are independently of each other hydrogen or methyl. The method of claim 17,
In Formula 15, T is -CH ₂ CH _2- , -CH ₂ CH (C ₆ H ₅ )-, -CH ₂ CH (CO ₂ Me)-, -CH ₂ CH (Cl)-or -CH ₂ C ( Me) (CO ₂ Me) —; R ¹²¹ is hydrogen or methyl; J is -CO _2- , R ^e1 to R ^e4 are each independently hydrogen or methyl block copolymer compound.

Images